Defects In MoS2 Research Articles

Electrostatic Screening of Charged Defects in Monolayer MoS2.

Defects in monolayer transition-metal dichalcogenides (TMDCs) may lead to unintentional doping, charge-carrier trapping, and nonradiative recombination. These effects impair electronic and optoelectronic technologies. Here we show that charged defects in MoS2 monolayers can be effectively screened when they are in contact with an ionic liquid (IL), leading to an increase in photoluminescence (PL) yield by up to two orders of magnitude. The extent of this PL enhancement by the IL correlates with the brightness of each pretreated sample. We propose the existence of two classes of nonradiative recombination centers in monolayer MoS2: (i) charged defects that relate to unintentional doping and may be electrostatically screened by ILs and (ii) neutral defects that remain unaffected by the presence of ILs.

Enhanced dielectric deposition on single-layer MoS2 with low damage using remote N2 plasma treatment

Using remote N2 plasma treatment to promote dielectric deposition on the dangling-bond free MoS2 is explored for the first time. The N2 plasma induced damages are systematically studied by the defect-sensitive acoustic-phonon Raman of single-layer MoS2, with samples undergoing O2 plasma treatment as a comparison. O2 plasma treatment causes defects in MoS2 mainly by oxidizing MoS2 along the already defective sites (most likely the flake edges), which results in the layer oxidation of MoS2. In contrast, N2 plasma causes defects in MoS2 mainly by straining and mechanically distorting the MoS2 layers first. Owing to the relatively strong MoS2–substrate interaction and chemical inertness of MoS2 in N2 plasma, single-layer MoS2 shows great stability in N2 plasma and only stable point defects are introduced after long-duration N2 plasma exposure. Considering the enormous vulnerability of single-layer MoS2 in O2 plasma and the excellent stability of single-layer MoS2 in N2 plasma, the remote N2 plasma treatment shows great advantage as surface functionalization to promote dielectric deposition on single-layer MoS2.

Improving the electrical performance of MoS2 by mild oxygen plasma treatment

Two-dimensional (2D) molybdenum disulfide (MoS2) is considered as a promising candidate for electronic and optoelectronic devices. However, structural defects in MoS2 are widely reported and can greatly degrade its electrical and optical properties. In this work, we investigate the structural defects in MoS2 by low temperature photoluminescence (PL) spectroscopy and study their effects on the electrical performance, i.e. carrier mobility. We also adopt the mild oxygen plasma treatment to repair the structural defects and found that the carrier mobility of monolayer MoS2 can be greatly improved. This work would therefore offer a practical route to improve the performance of 2D dichalcogenide-based electrical and optoelectronic devices.

Experimental detection of active defects in few layers MoS2 through random telegraphic signals analysis observed in its FET characteristics

Transition-metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2), are expected to be promising for next generation device applications. The existence of sulfur vacancies formed in MoS2, however, will potentially make devices unstable and problematic. Random telegraphic signals (RTSs) have often been studied in small area Si metal-oxide-semiconductor field-effect transistors (MOSFETs) to identify the carrier capture and emission processes at defects. In this paper, we have systemically analyzed RTSs observed in atomically thin layer MoS2 FETs. Several types of RTSs have been analyzed. One is the simple on/off type of telegraphic signals, the second is multilevel telegraphic signals with a superposition of the simple signals, and the third is multilevel telegraphic signals that are correlated with each other. The last one is discussed from the viewpoint of the defect–defect interaction in MoS2 FETs with a weak screening in atomically confined two-dimensional electron-gas systems. Furthermore, the position of defects causing RTSs has also been investigated by preparing MoS2 FETs with multi-probes. The electron beam was locally irradiated to intentionally generate defects in the MoS2 channel. It is clearly demonstrated that the MoS2 channel is one of the RTS origins. RTS analysis enables us to analyze the defect dynamics of TMD devices.

Probing the intrinsic optical quality of CVD grown MoS2

Optical emission efficiency of two-dimensional layered transition metal dichalcogenides (TMDs) is one of the most important parameters affecting their optoelectronic performance. The optimization of the growth parameters by chemical vapor deposition (CVD) to achieve optoelectronic-grade quality TMDs is, therefore, highly desirable. Here, we present a systematic photoluminescence (PL) spectroscopic approach to assess the intrinsic optical and crystalline quality of CVD grown MoS2 (CVD MoS2). We propose the use of the intensity ratio between the PL measured in air and vacuum as an effective way to monitor the intrinsic optical quality of CVD MoS2. Low-temperature PL measurements are also used to evaluate the structural defects in MoS2, via defect-associated bound exciton emission, which well correlates with the field-effect carrier mobility of MoS2 grown at different temperatures. This work therefore provides a sensitive, noninvasive method to characterize the optical properties of TMDs, allowing the tuning of the growth parameters for the development of optoelectronic devices.

Selective hydrodesulfurization of gasoline on Co/MoS2 ± x catalyst: Effect of sulfur defects in MoS2 ± x

To improve the hydrodesulfurization activity while to minimize the hydrogen consumption from the hydrogenation of olefins is of importance for the deep desulfurization of gasoline. Herein, a series of Co/MoS2±x catalysts were prepared by impregnating Co-promoter to MoS2±x (x≤0.06) with controllably varied S/Mo atomic ratio. The S/Mo atomic ratio of MoS2±x in Co/MoS2±x catalysts influences the catalytic performance of Co/MoS2±x in simultaneously thiophene hydrodesulfurization (HDS) and cyclohexene hydrogenation (HYD) reactions. With decreasing the S/Mo atomic ratio in Co/MoS2±x, the HDS selectivity factor (kHDS/kHYD) increases to two times (from 37 to 89), although the catalytic activities of HDS and HYD decrease due to the low content of CoMoS phase. The higher selectivity of Co/MoS2±x with lower S/Mo atomic ratio could be well explained by larger size of sulfide crystallites exposed lower corner sites. Therefore, a high HDS selectivity catalyst could be developed by properly controlling the crystal size of sulfide crystallites.

Point Defects and Grain Boundaries in Rotationally Commensurate MoS2 on Epitaxial Graphene

With reduced degrees of freedom, structural defects are expected to play a greater role in two-dimensional materials in comparison to their bulk counterparts. In particular, mechanical strength, electronic properties, and chemical reactivity are strongly affected by crystal imperfections in the atomically thin limit. Here, ultra-high vacuum (UHV) scanning tunneling microscopy (STM) and spectroscopy (STS) are employed to interrogate point and line defects in monolayer MoS2 grown on epitaxial graphene (EG) at the atomic scale. Five types of point defects are observed with the majority species showing apparent structures that are consistent with vacancy and interstitial models. The total defect density is observed to be lower than MoS2 grown on other substrates, and is likely attributed to the van der Waals epitaxy of MoS2 on EG. Grain boundaries (GBs) with 30{\deg} and 60{\deg} tilt angles resulting from the rotational commensurability of MoS2 on EG are more easily resolved by STM than atomic force microscopy at similar scales due to the enhanced contrast from their distinct electronic states. For example, band gap reduction to ~0.8 eV and ~0.5 eV is observed with STS for 30{\deg} and 60{\deg} GBs, respectively. In addition, atomic resolution STM images of these GBs are found to agree well with proposed structure models. This work offers quantitative insight into the structure and properties of common defects in MoS2, and suggests pathways for tailoring the performance of MoS2/graphene heterostructures via defect engineering.

Probing Defect‐Induced Midgap States in MoS2 Through Graphene–MoS2 Heterostructures

Crystalline defects in MoS2 may induce midgap states, resulting in low carrier mobility. These midgap states are usually difficult to probe by conventional transport measurement. The quantum capacitance of single‐layer graphene is sensitive to defect‐induced states near the Dirac point, at which the density of states is extremely low. It is reported that the hexagonal‐boron nitride/graphene/MoS2 sandwich structure facilitates the exploration of the properties of those midgap states in MoS2. Comparative results of the quantum capacitance of pristine graphene indicate the presence of several midgap states with distinct features. Some of these states donate electrons while some states lead to localization of electrons. It is believed that these midgap states originate from intrinsic point defects such as sulfur vacancies, which have a significant impact on the property of the MoS2/graphene interface. They are responsible for the contact problems of metal/MoS­2 interfaces.

Transition metal chalcogenides: ultrathin inorganic materials with tunable electronic properties.

CONSPECTUS: After the discovery of graphene and the development of powerful exfoliation techniques, experimental preparation of two-dimensional (2D) crystals can be expected for any layered material that is known to chemistry. Besides graphene and hexagonal boron nitride (h-BN), transition metal chalcogenides (TMC) are among the most studied ultrathin materials. In particular, single-layer MoS2, a direct band gap semiconductor with ∼1.9 eV energy gap, is popular in physics and nanoelectronics, because it nicely complements semimetallic graphene and insulating h-BN monolayer as a construction component for flexible 2D electronics and because it was already successfully applied in the laboratory as basis material for transistors and other electronic and optoelectronic devices. Two-dimensional crystals are subject to significant quantum confinement: compared with their parent layered 3D material, they show different structural, electronic, and optical properties, such as spontaneous rippling as free-standing monolayer, significant changes of the electronic band structure, giant spin-orbit splitting, and enhanced photoluminescence. Most of those properties are intrinsic for the monolayer and already absent for two-layer stacks of the same 2D crystal. For example, single-layer MoS2 is a direct band gap semiconductor with spin-orbit splitting of 150 meV in the valence band, while the bilayer of the same material is an indirect band gap semiconductor without observable spin-orbit splitting. All these properties have been observed experimentally and are in excellent agreement with calculations based on density-functional theory. This Account reports theoretical studies of a subgroup of transition metal dichalcogenides with the composition MX2, with M = Mo, or W and X = Se or S, also referred to as "MoWSeS materials". Results on the electronic structure, quantum confinement, spin-orbit coupling, spontaneous monolayer rippling, and change of electronic properties in the presence of an external electric field are reported. While all materials of the MoWSeS family share the same qualitative properties, their individual values can differ strongly, for example, the spin-orbit splitting in WSe2 reaches the value of 428 meV, nearly three times that of MoS2. Further, we discuss the effect of strain on the electronic properties (straintronics). While MoWSeS single layers are very robust against external electric fields, bilayers show a linear reduction of the band gap, even reaching a semiconductor-metal phase transition, and an increase of the spin-orbit splitting from zero to the monolayer value at rather small fields. Strain is yet another possibility to control the band gap in a linear way, and MoWSeS monolayers become metallic at strain values of ∼10%. The density-functional based tight-binding model is a useful tool to investigate the electronic and structural properties, including electron conductance, of large MoS2 structures, which show spontaneous rippling in finite-temperature molecular dynamics simulations. Structural defects in MoS2 result in anisotropy of the electric conductivity. Finally, DFT predictions on the properties of noble metal dichalcogenides are presented. Most strikingly, 1T PdS2 is an indirect band gap semiconductor in its monolayer form but becomes metallic as a bilayer.

Synthesis and defect investigation of two-dimensional molybdenum disulfide atomic layers.

CONSPECTUS: The unique physical properties of two-dimensional (2D) molybdenum disulfide (MoS2) and its promising applications in future optoelectronics have motivated an extensive study of its physical properties. However, a major limiting factor in investigation of 2D MoS2 is its large area and high quality preparation. The existence of various types of defects in MoS2 also makes the characterization of defect types and the understanding of their roles in the physical properties of this material of critical importance. In this Account, we review the progress in the development of synthetic approaches for preparation of 2D MoS2 and the understanding of the role of defects in its electronic and optical properties. We first examine our research efforts in understanding exfoliation, direct sulfurization, and chemical vapor deposition (CVD) of MoS2 monolayers as main approaches for preparation of such atomic layers. Recognizing that a natural consequence of the synthetic approaches is the addition of sources of defects, we initially focus on identifying these imperfections with intrinsic and extrinsic origins in CVD MoS2. We reveal the predominant types of point and grain boundary defects in the crystal structure of polycrystalline MoS2 using transmission electron microscopy (TEM) and understand how they modify the electronic band structure of this material using first-principles-calculations. Our observations and calculations reveal the main types of vacancy defects, substitutional defects, and dislocation cores at the grain boundaries (GBs) of MoS2. Since the sources of defects in two-dimensional atomic layers can, in principle, be controlled and studied with more precision compared with their bulk counterparts, understanding their roles in the physical properties of this material may provide opportunities for changing their properties. Therefore, we next examine the general electronic properties of single-crystalline 2D MoS2 and study the role of GBs in the electrical transport and photoluminescence properties of its polycrystalline counterparts. These results reveal the important role played by point defects and GBs in affecting charge carrier mobility and excitonic properties of these atomic layers. In addition to the intrinsic defects, growth process induced substrate impurities and strain induced band structure perturbations are revealed as major sources of disorder in CVD grown 2D MoS2. We further explore substrate defects for modification and control of electronic and optical properties of 2D MoS2 through interface engineering. Self-assembled monolayer based interface modification, as a versatile technique adaptable to different conventional and flexible substrates, is used to promote significant tunability in the key MoS2 field-effect device parameters. This approach provides a powerful tool for modification of native substrate defect characteristics and allows for a wide range of property modulations. Our results signify the role of intrinsic and extrinsic defects in the physical properties of MoS2 and unveil strategies that can utilize these characteristics.

Defect-Dominated Doping and Contact Resistance in MoS2

Achieving low resistance contacts is vital for the realization of nanoelectronic devices based on transition metal dichalcogenides. We find that intrinsic defects in MoS2 dominate the metal/MoS2 contact resistance and provide a low Schottky barrier independent of metal contact work function. Furthermore, we show that MoS2 can exhibit both n-type and p-type conduction at different points on a same sample. We identify these regions independently by complementary characterization techniques and show how the Fermi level can shift by 1 eV over tens of nanometers in spatial resolution. We find that these variations in doping are defect-chemistry-related and are independent of contact metal. This raises questions on previous reports of metal-induced doping of MoS2 since the same metal in contact with MoS2 can exhibit both n- and p-type behavior. These results may provide a potential route for achieving low electron and hole Schottky barrier contacts with a single metal deposition.